In this work, a non-chromatographic procedure for the on-line determination of ultratraces of V(V) and V(IV) is presented. The method involves a solid phase extraction-flow injection system coupled to electrothermal atomic absorption spectrometry (SPE-FI-ETAAS). The system holds two microcolumns (MC) set in parallel and filled with lab-made mesoporous silica functionalized with 3-aminopropyltriethoxy silane (APS) and mesoporous silica MCM-41, respectively. The pre-concentration of V(V) is performed by sorption onto the first MC (C1) filled with APS at pH 3, whilst that of V(IV) is performed by sorption onto the second column (C2) filled with mesoporous silica MCM-41 at pH 5. Aqueous samples containing both analytes are loaded and, after pre-concentration (pre-concentration factor PCF=10, sorption flow rate=1 mL min(-1), sorption time=10 min), they are eluted in separate vessels with hydroxylammonium chloride (HC) 0.1 mol L(-1) in HCl 0.5 mol L(-1) (elution volume=1 mL, elution flow rate=0.5 mL min(-1)). Afterwards, both analytes are determined through ETAAS with graphite furnace. Under optimized conditions, the main analytical figures of merit for V(V) and V(IV) are, respectively: detection limits (3s): 0.5 and 0.6 microg L(-1), linear range: 2-100 microg L(-1) (both analytes), sensitivity: 0.015 and 0.013 microg(-1)L and sample throughput: 6h(-1) (both analytes). Recoveries of both species were assayed in different water samples. Validation was performed through certified reference materials for ultratraces of total vanadium in river water.